UC Berkeley UC Berkeley Electronic Theses and Dissertations Title Encapsulating Metal Clusters and Acid Sites within Small Voids: Synthetic Strategies and Catalytic Consequences Permalink https://escholarship.org/uc/item/8xv8d3dh Author Goel, Sarika Publication Date 2015 Peer reviewed|Thesis/dissertation eScholarship.org Powered by the California Digital Library University of California Encapsulating Metal Clusters and Acid Sites within Small Voids: Synthetic Strategies and Catalytic Consequences by Sarika Goel A dissertation submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Chemical Engineering in the Graduate Division of the University of California, Berkeley Committee in charge: Professor Enrique Iglesia, Chair Professor Alexander Katz Professor Jeffrey R. Long Summer 2015 Encapsulating Metal Clusters and Acid Sites within Small Voids: Synthetic Strategies and Catalytic Consequences Copyright 2015 by Sarika Goel Abstract Encapsulating Metal Clusters and Acid Sites within Small Voids: Synthetic Strategies and Catalytic Consequences by Sarika Goel Doctor of Philosophy in Chemical Engineering University of California, Berkeley Professor Enrique Iglesia, Chair The selective encapsulation of metal clusters within zeolites can be used to prepare clusters that are uniform in diameter and to protect them against sintering and contact with feed impurities, while concurrently allowing active sites to select reactants based on their molecular size, thus conferring enzyme-like specificity to chemical catalysis. The apertures in small and medium-pore zeolites preclude the use of post-synthetic protocols to encapsulate the relevant metal precursors because cationic or anionic precursors with their charge-balancing double layer and gaseous complexes cannot diffuse through their windows or channels. We have developed general strategies to encapsulate metal clusters within small-pore zeolites by using metal precursors stabilized by ammonia or organic amine ligands, which stabilize metal precursors against their premature precipitation at the high temperature and pH conditions required for the hydrothermal synthesis of the target zeolite structures and favor interactions between metal precursors and incipient aluminosilicate nuclei during the self-assembly of microporous frameworks. When synthesis temperatures were higher than 400 K, available ligands were unable to prevent the premature precipitation of the metal precursors. In such cases, encapsulation was achieved instead via interzeolite transformations after successfully encapsulating metal precursors or clusters via post-synthesis exchange or ligand protection into parent zeolites and subsequently converting them into the target structures while retaining the encapsulated clusters or precursors. Such strategies led to the successful selective encapsulation of a wide range of metal clusters (Pt, Pd, Ru, Rh, Ir, Re, and Ag) within small-pore (SOD (sodalite), LTA (Linde type A (zeolite A)), GIS (gismondine), and ANA (analcime)) and medium-pore (MFI (ZSM-5)) zeolites. These protocols provide novel and diverse mechanism-based strategies for the design of catalysts with protected active sites. We have demonstrated the selectivity of the encapsulation processes by combining transmission electron microscopy and chemisorptive titrations with rigorous catalytic assessments of the ability of these materials to catalyze reactions of small molecules, which can access the intracrystalline voids, but not of larger molecules that cannot access the metal clusters within such voids. The selective confinement of clusters also prevented their contact with sulfur compounds (e.g., thiophene and H2S), thus allowing reactions to occur at conditions that otherwise render unconfined clusters unreactive. 1 We have also developed synthetic protocols and guiding principles, inspired by mechanistic considerations, for the synthesis of zeolites via interzeolite transformations without the use of organic structure-directing agents (OSDA). More specifically, we have synthesized high-silica MFI (ZSM-5), CHA (chabazite), STF (SSZ-35) and MTW (ZSM-12) zeolites from FAU (faujasite) or BEA (beta) parent materials. Structures with lower framework densities (FAU or BEA) were successfully transformed into thermodynamically-favored, more stable structures with higher framework densities (MFI, CHA, STF, and MTW); to date, target materials with higher Si/Al ratios (Si/Al >10) have not been synthesized via interzeolite transformations without the aid of the OSDA species used to discover these zeolite structures and deemed essential up until now for their successful synthesis. Overcoming kinetic hurdles in such transformations required either the presence of common composite building units (CBU) between parent and target structures or, in their absence, the introduction of small amount of seeds of the daughter structures. The NaOH/SiO2 ratio, H2O/SiO2 ratio and Al content in reagents are used to enforce synchronization between the swelling and local restructuring within parent zeolite domains with the spalling of fragments or building units from seeds of the target structure. The pseudomorphic nature of these seed-mediated transformations, which conserve the volume occupied by the parent crystals and lead to similar size and crystal shape in products, reflect incipient nucleation of target structures occurring at the outer regions of the parent domains and lead to the formation of mesoporosity as a natural consequence of the space-conserving nature of these structural changes and of the higher density of the daughter frameworks. The synthesis mechanism and the guidelines developed enable us to enforce conditions required for the formation of zeolites that previously required OSDA species for their synthesis, thus expanding to a significant extent the diversity of zeolite frameworks that are accessible via these synthesis protocols and providing potential savings in the time and cost involved in the synthesis of some of these zeolite structures. 2 To my family for their unconditional love and support i Table of Contents List of Figures ............................................................................................................................... vi List of Tables ................................................................................................................................ xi List of Schemes ........................................................................................................................... xiii Acknowledgments........................................................................................................................ xiv Chapter 1: Introduction to Metal Clusters and Acid Sites Encapsulation within Zeolite Voids....1 1.1 Introduction ...........................................................................................................................1 1.2 References .............................................................................................................................4 Chapter 2: Hydrothermal Synthesis of LTA-Encapsulated Metal Clusters and Consequences for Catalyst Stability, Reactivity and Selectivity...................................................................................5 Abstract .......................................................................................................................................5 2.1 Introduction ...........................................................................................................................5 2.2 Methods.................................................................................................................................6 2.2.1 Materials .....................................................................................................................6 2.2.2 Catalyst Synthesis .......................................................................................................6 2.2.2.1 Metal-Free LTA ...............................................................................................6 2.2.2.2 Metal Clusters Encapsulated within LTA .......................................................7 2.2.3 Characterization ..........................................................................................................8 2.2.4 Catalytic Reactions .....................................................................................................8 2.3 Results and Discussion ........................................................................................................9 2.3.1 Size and Stability of Metal Clusters ..........................................................................10 2.3.2 Reactant Selectivity in Alkanol Dehydrogenation and Alkene Hydrogenation .......12 2.3.2.1 Oxidative Dehydrogenation (ODH) of Alkanols ..........................................13 2.3.2.2 Hydrogenation (HD) of Alkenes ...................................................................13 2.3.3 Protection of Metal Clusters from Contact with Larger Poisons during Catalysis ...14 2.4 Conclusions ........................................................................................................................15 2.5 Acknowledgments ..............................................................................................................15 2.6 Figures, Tables and Scheme ..............................................................................................16 2.7 Supporting Information